The combustion behavior of ammonium perchlorate (AP) determines the combustion performance of the propellant to a certain extent. Not only the addition of catalyst can change the thermal decomposition performance of AP, but also the combination mode of catalyst and AP can change the thermal decomposition behavior of AP. In this study, different catalysts and AP were prepared by mechanical mixing and spray drying composite, respectively. The results showed that compared with mechanical mixing, spray drying composites showed better catalytic performance on the thermal decomposition of AP. Compared with pure AP, all catalysts passivated the low-temperature decomposition process of AP, while catalyzed the high-temperature decomposition process of AP. At the heating rate of 5 K/min, AP@GO/Cu-MOF-300 makes the high temperature decomposition temperature of AP advance by 105.49 ℃, the activation energy decreases from 194.66 to 101.51 kJ/mol, and the heat release increases nearly four times.